CN109100402B - Method for depositing platinum monoatomic compound and application - Google Patents
Method for depositing platinum monoatomic compound and application Download PDFInfo
- Publication number
- CN109100402B CN109100402B CN201810795400.4A CN201810795400A CN109100402B CN 109100402 B CN109100402 B CN 109100402B CN 201810795400 A CN201810795400 A CN 201810795400A CN 109100402 B CN109100402 B CN 109100402B
- Authority
- CN
- China
- Prior art keywords
- metal phosphide
- platinum
- depositing
- electrode
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for depositing platinum monoatomic atoms, a compound and application, wherein the method for depositing the platinum monoatomic atoms comprises the following steps: dispersing the metal phosphide nanosheets in a solvent to prepare a dispersion liquid; dropping the dispersion liquid on carbon paper, drying to be used as a working electrode, taking a saturated calomel electrode as a reference electrode, and taking a platinum electrode as a counter electrode; preparing electrolyte, setting up an electrolytic cell, setting a certain voltage and a certain number of circulating circles, and depositing on the surface of the metal phosphide nano-sheet to obtain the platinum monoatomic layer. The method disclosed by the invention does not need complex equipment, is simple to operate, has a wide application range, is suitable for various metal phosphide materials, remarkably improves the catalytic performance of the prepared compound, and provides a new thought for researching monatomic catalysis.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for depositing platinum monoatomic atoms, a compound and application.
Background
At present, the development of a high-efficiency catalyst is one of the main research contents in the field of catalysts. The supported metal catalyst has excellent catalytic performance, and the catalytic performance of the supported catalyst is closely related to the size of the metal active component on the carrier. In order to optimize the catalytic effect of supported metal catalysts, the size of the active metal is becoming smaller. A monatomic catalyst is a catalyst in which the metal is uniformly distributed in the form of a single atom on a support.
The single atom Pt/FeO was first prepared in 2011 from the major chemical project groupxCatalyst (Nature chemistry, 2011,3(8):634-641) which achieves high catalytic activity and stability in CO oxidation and CO selective oxidation reactions, and thus proposes the concept of monatomic catalysis. In 2012, the group of subjects e. Charles h.sykes, which uses monoatomic Pd dispersed on Cu surface, characterized the atom dispersed catalyst by STM and the like, has good selectivity for hydrogenation reaction (Science, 2012,335(6073): 1209-. In 2014, the package letter and the subject group prepared Fe/SiO with atomic scale dispersion2The oxygen-free preparation of ethylene from methane and the prevention of formation have made important progress (Sciense, 2014,334(6184): 616-619.2016, Zhengnan peak subject group Pd/TiO synthesized by simple photochemical method2The monoatomic catalyst has excellent activity in the hydrogenation of olefins (Science, 2016,352(6287): 797-800). However, the preparation method of the monatomic catalyst in the prior art has the problems of complex equipment, large difficulty in experimental operation, small application range and low catalytic performance of the prepared monatomic catalyst.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method, a compound and an application for depositing platinum monoatomic atoms, and aims to solve the problems of complex equipment, high operation difficulty, small application range and low catalytic performance of the prepared monoatomic catalyst in the prior art.
The technical scheme of the invention is as follows:
a method for depositing platinum monoatomic atoms on the surface of a metal phosphide nanosheet, comprising the steps of:
dispersing the metal phosphide nanosheets in a solvent to prepare a dispersion liquid;
dropping the dispersion liquid on carbon paper, drying to be used as a working electrode, taking a saturated calomel electrode as a reference electrode, and taking a platinum electrode as a counter electrode;
preparing electrolyte, setting up an electrolytic cell, setting a certain voltage and a certain number of circulating circles, and depositing on the surface of the metal phosphide nano-sheet to obtain the platinum monoatomic layer.
The method for depositing the platinum monatomic on the surface of the metal phosphide nanosheet is characterized in that the metal element in the metal phosphide nanosheet is one or more of a VIII-group metal element, an IVB-group metal element, a VB-group metal element, a VIB-group metal element, a VIIB-group metal element and a IIB-group metal element.
The method for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets is characterized in that the metal elements in the metal phosphide nanosheets are one or more of iron, cobalt, nickel, manganese, zinc, chromium, tin, lead and molybdenum.
The method for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets is characterized in that the solvent is an isopropanol solution containing naphthol.
The method for depositing the platinum monoatomic layer on the surface of the metal phosphide nanosheet is characterized in that the volume ratio of isopropanol to naphthol is 10: 1-1000: 1.
The method for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets comprises the step of depositing a dispersion liquid with the mass concentration of 1-5 mg/mL.
The method for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets is characterized in that the carbon paper is 1 square centimeter carbon paper; and dropwise adding the dispersion liquid to the carbon paper, wherein the volume of the dispersion liquid is 50-500 mu L.
The method for depositing the platinum monoatomic layer on the surface of the metal phosphide nanosheet is characterized in that the electrolyte is an acidic electrolyte with the pH of 1-3, the voltage is 0-1.3V, and the number of cycles is 1000-15000.
A composite, wherein the composite is prepared by the method as described above; the composite comprises metal phosphide nanosheets and platinum monatomics grown on the surface of the metal phosphide nanosheets.
Use of a composite as described above, wherein the composite is used for electrocatalytic water splitting.
Has the advantages that: the invention provides a method for depositing platinum monatomic on the surface of a metal phosphide nanosheet. The method disclosed by the invention does not need complex equipment, is simple to operate, has a wide application range, is suitable for various metal phosphide materials, remarkably improves the catalytic performance of the prepared compound, and provides a new thought for researching monatomic catalysis.
Drawings
FIG. 1 is a schematic flow chart of the deposition of platinum monoatomic layer according to example 1 of the present invention.
FIG. 2 is Co prepared in example 1 of the present invention0.5Ni0.5PxTransmission pattern of nanoplatelets.
FIG. 3 is a diagram of Pt-Co prepared in example 1 of the present invention0.5Ni0.5PxLSV profile of OER of the complex.
FIG. 4 is a diagram of Pt-Co prepared in example 2 of the present invention0.25Ni0.75PxLSV profile of HER of complex.
FIG. 5 is a diagram of Pt-Co prepared in example 3 of the present invention0.25Ni0.75PxLSV profile of HER of complex.
FIG. 6 is a diagram of Pt-CoP prepared in example 4 of the present inventionxLSV profile of HER of complex.
Detailed Description
The present invention provides a method, a composition and an application for depositing platinum monoatomic atoms, and the present invention is further described in detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for depositing platinum monoatomic atoms on the surface of a metal phosphide nanosheet, which comprises the following steps:
step A, dispersing metal phosphide nanosheets in a solvent to prepare a dispersion liquid;
b, dropping the dispersion liquid on carbon paper, drying to be used as a working electrode, taking a saturated calomel electrode as a reference electrode, and taking a platinum electrode as a counter electrode;
and step C, preparing electrolyte, setting up an electrolytic cell, setting a certain voltage and a certain number of circulating circles, and depositing on the surface of the metal phosphide nanosheet to obtain the platinum monatomic.
The mechanism of the invention for obtaining the platinum monoatomic on the surface of the metal phosphide nanosheet by deposition is as follows: the platinum electrode generates the decomposition of platinum monoatomic atoms in the electrical cycle process under certain conditions, the separated platinum monoatomic atoms are deposited on the metal phosphide nano-sheets under the action of potential, and the platinum monoatomic atoms are deposited on the surfaces of the metal phosphide nano-sheets. The method for depositing the platinum monoatomic layer does not need complex equipment, is simple to operate and has low cost. More importantly, the method for electrochemically depositing the platinum monoatomic atom by using the three-electrode system can deposit the platinum monoatomic atom on the surfaces of various metal phosphide nano-sheets so as to enhance the catalytic performance of the platinum monoatomic atom.
The step A of the invention specifically comprises the following steps:
a1, preparing white calcium silicate hard nanowire powder into calcium silicate hard nanowire dispersion liquid, adding metal chloride into the calcium silicate hard nanowire dispersion liquid, magnetically stirring until the solution becomes transparent, then carrying out water bath reaction, cooling at room temperature, washing the obtained product with water for multiple times, washing the product with ethanol for multiple times, and drying the product in a vacuum drying oven to obtain amorphous metal hydroxide nanosheet powder;
a2, respectively adding sodium dihydrogen phosphite and amorphous metal hydroxide nanosheet powder at the head and tail of a small porcelain boat, uniformly heating in an inert gas (such as argon), calcining at a high temperature of 200-400 ℃, and cooling to obtain metal phosphide nanosheets;
a3, weighing a proper amount of metal phosphide nanosheets, dispersing the nanosheets in a solvent, and performing ultrasonic dispersion to prepare a dispersion liquid.
Preferably, the metal elements in the metal phosphide nanosheets are one or more of group VIII metal elements, group IVB metal elements, group VB metal elements, group VIB metal elements, group VIIB metal elements, group IIB metal elements and the like. According to the invention, a method for electrochemically depositing the monoatomic atoms by using a three-electrode system can be used for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets, so that the platinum monoatomic catalyst can be successfully prepared. More preferably, the metal element in the metal phosphide is one or more of iron, cobalt, nickel, manganese, zinc, chromium, tin, lead, molybdenum and the like. The platinum monatomic catalyst prepared by adopting the preferable metal phosphide nanosheets has more excellent catalytic performance.
The metal phosphide nanosheet has the characteristic of high specific surface area, so that more active sites can be provided, the utilization rate of platinum atoms can be improved to the greatest extent after single atoms are loaded, and the catalytic activity of the metal phosphide nanosheet is improved. The metal phosphide nanosheet disclosed by the invention has a two-dimensional ultrathin lamellar structure, and can keep better stability and electrocatalysis performance under an acidic condition. The three-electrode system electrochemical deposition method is a preparation method with long time, the stability of the metal phosphide nanosheet is beneficial to the smooth proceeding of the electrodeposition process, and the two-dimensional ultrathin lamellar structure is also beneficial to the deposition of platinum atoms.
Preferably, the solvent is an isopropanol solution containing naphthol. According to the invention, a proper amount of naphthol is added into isopropanol, so that metal phosphide can be adhered to the surface of an electrode, and the contact resistance between a catalyst and the electrode is increased greatly due to the high content of naphthol, which is not beneficial to the implementation of an electrochemical deposition process. Preferably, the volume ratio of the isopropanol to the naphthol is 10: 1-1000: 1. Most preferably, the volume ratio of the isopropanol to the naphthol is 1000:7, and the attachment amount of the metal phosphide nanosheets on the surface of the carbon paper can be remarkably improved in an isopropanol solution containing naphthol with the optimal ratio, so that the effect of depositing the platinum atom catalyst on the metal phosphide nanosheets by using a three-electrode system in the subsequent step is improved.
Preferably, the concentration of the dispersion liquid is 1-5 mg/mL, and the optimal concentration is 2 mg/mL. The method controls the concentration of the dispersion liquid within a proper range, can ensure that the metal phosphide nanosheet powder can be uniformly dispersed, and is convenient for dropwise adding of the catalyst on the surface of the carbon paper.
Preferably, the ultrasonic dispersion time is 10-100 min, and the optimal time is 60 min. And rapidly dispersing the metal phosphide within the ultrasonic dispersion time to obtain a uniform and stable metal phosphide nanosheet solution.
In the step B, the carbon paper is 1 square centimeter carbon paper, and the dropping volume of the dispersion liquid corresponding to the carbon paper is 50-500 mu L. The dropping volume of the metal phosphide nanosheets determines the loading amount of the surface catalyst. According to the invention, the dropping volume of the metal phosphide nanosheets is controlled, so that the loading capacity is controlled within a proper range, and the catalytic performance of the metal phosphide nanosheets can be improved to the maximum extent while the electrochemical deposition time is saved.
In the step C, the electrolyte of the present invention may be a neutral or acidic electrolyte. Preferably, the electrolyte is an acidic electrolyte, since deposition under acidic conditions can increase the transfer rate of platinum monoatomic atoms, contributing to the deposition efficiency of platinum monoatomic atoms on the metal phosphide nanosheets.
Preferably, the pH value of the acidic electrolyte is 1-3, the voltage is 0-1.3V, and the number of cycles is 1000-15000. The acidic pH, the voltage and the number of circulating circles ensure that the deposition process is fully carried out, and the problem of reduction of the catalytic performance of the platinum monatomic catalyst caused by insufficient deposition process is solved.
The invention provides a compound prepared by the method. The compound of the invention has the structural characteristics that: the composite comprises metal phosphide nanosheets and platinum monatomics grown on the surface of the metal phosphide nanosheets.
The invention also provides the application of the compound, and the compound is applied to electrocatalytic water decomposition. The compound prepared by the invention has the characteristics of high catalytic activity and high utilization rate of platinum atoms, and can be applied to electrocatalytic water decomposition.
The technical solution of the present invention will be explained below by specific examples.
Example 1
1、Co0.5Ni0.5PxSynthesis of nanoplatelets
Preparing 0.1 wt% hard calcium silicate nanowire dispersion liquid from white hard calcium silicate nanowire powder, adding 3 mmol of cobalt chloride hexahydrate and nickel chloride hexahydrate into 50mL of hard calcium silicate nanowire dispersion liquid, wherein the total concentration of cobalt ions and nickel ions is 0.06 mol/L, magnetically stirring for 0.5 h until the solution becomes transparent, carrying out water bath reaction for 3 h at the temperature of 80 ℃, cooling at room temperature, washing the obtained product with water for 3 times, washing with ethanol for 1 time, drying in a vacuum drying oven at the temperature of 60 ℃ for 6 h, and preparing Co0.5Ni0.5（OH）2Nanosheet powder.
Adding 50 mg of sodium dihydrogen phosphite and 10 mg of Co into the head and tail of the small porcelain boat0.5Ni0.5（OH）2Heating the nanosheet powder to 300 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, and calcining at a high temperature to obtain Co0.5Ni0.5PxNanosheets.
2. Deposition of platinum monoatomic layer
6mg of Co are weighed0.5Ni0.5PxDispersing the nano-sheets in 2mL of isopropanol solution containing naphthol (the volume ratio of isopropanol to naphthol is 1000: 7), ultrasonically dispersing for 1h, transferring 100mL of dispersed liquid drops on carbon paper with the thickness of 1 square centimeter by using a liquid transfer gun, and drying at room temperature; preparing sulfuric acid with a molar concentration of 0.5moL/L as an electrolyte and containing Co0.5Ni0.5PxThe carbon paper of the nano sheet is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the voltage range is set to be-0.2 to-1.0V, the number of cycles is respectively set to be 2500, 5000, 7500 and 10000, and the Pt-Co is prepared0.5Ni0.5PxAnd (c) a complex.
Referring to fig. 1, fig. 1 is a schematic flow chart of the deposition of platinum monoatomic atoms according to the present embodiment. Wherein the prepared compound has the structural characteristics that: the platinum monoatomic atoms are uniformly distributed on the ultrathin metal phosphide nanosheets, and the ultrathin metal phosphide nanosheets loaded with the platinum monoatomic atoms vertically grow on the surface of the calcium silicate nanowire.
Referring to FIG. 2, FIG. 2 shows Co prepared in this example0.5Ni0.5PxTransmission pattern of nanoplatelets. As can be seen from FIG. 2, Co prepared in this example0.5Ni0.5PxThe nano sheet has a two-dimensional ultrathin nano sheet structure.
For the Pt-Co prepared in this example of the invention0.5Ni0.5PxThe composites were subjected to OER electrochemical testing.
Referring to FIG. 3, FIG. 3 shows 4 Pt-Co prepared in this example0.5Ni0.5PxLSV profile of OER of the complex. It can be seen from the figure that the OER electrochemical performance gradually increases with the increase of the number of cycles, the best electrochemical performance is obtained when the number of cycles is 2500, the improvement is significant compared with the improvement when the number of cycles is 0, and the electrochemical performance is basically the same when the number of cycles is 5000 and 7500. Therefore, at 2500 cycles, the Pt-Co0.5Ni0.5PxThe OER electrochemical performance of the composite is improved to the best degree.
Example 2
1、Co0.25Ni0.75PxSynthesis of nanoplatelets
Preparing 0.1 wt% hard calcium silicate nanowire dispersion liquid from white hard calcium silicate nanowire powder, adding 3 mmol of cobalt chloride hexahydrate and nickel chloride hexahydrate into 50mL of hard calcium silicate nanowire dispersion liquid, wherein the total concentration of cobalt ions and nickel ions is 0.06 mol/L, magnetically stirring for 0.5 h until the solution becomes transparent, carrying out water bath reaction for 3 h at the temperature of 80 ℃, cooling at room temperature, washing the obtained product with water for 3 times, washing with ethanol for 1 time, drying in a vacuum drying oven at the temperature of 60 ℃ for 6 h, and preparing Co0.25Ni0.75（OH）2Nanosheet powder.
Adding 50 mg of sodium dihydrogen phosphite and sodium dihydrogen phosphite into the head and tail of the small porcelain boat10 mg of Co0.5Ni0.5（OH）2Heating the nanosheet powder to 300 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, and calcining at a high temperature to obtain Co0.25Ni0.75PxNanosheets.
2. Deposition of platinum monoatomic layer
6mg of Co are weighed0.25Ni0.75PxDispersing the nano-sheets in 2mL of isopropanol solution containing naphthol (the volume ratio of isopropanol to naphthol is 100: 1), ultrasonically dispersing for 1h, respectively transferring 25mL, 50mL, 75mL, 100mL and 200mL of dispersed liquid drops on carbon paper with the square centimeter by using a liquid transfer gun, and drying at room temperature; preparing sulfuric acid with a molar concentration of 0.5moL/L as an electrolyte and containing Co0.25Ni0.75PxThe carbon paper of the nano sheet is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the voltage range is set to be-0.2 to-1.0V, the number of circulating turns is set to be 2500, and the Pt-Co nano-material is prepared0.25Ni0.75PxAnd (c) a complex.
For the Pt-Co prepared in this example0.25Ni0.75PxThe complexes were subjected to HER electrochemical testing.
Referring to FIG. 4, FIG. 4 shows 5 kinds of Pt-Co prepared in this example separately0.25Ni0.75PxLSV profile of HER complex tested. It can be seen from the figure that Co is associated with carbon paper0.25Ni0.75PxThe HER electrochemical test performance of the nanosheet is gradually improved due to the increase of the loading amount of the nanosheet, but the test performance of the nanosheet begins to be deteriorated when the loading amount reaches 200mL, which shows that the test performance is also reduced due to the overhigh loading amount. From the graph, it can be seen that Pt-Co is supported at a load of 100mL0.25Ni0.75PxThe HER electrochemical test performance of the complex was best.
Example 3
1、Co0.25Ni0.75PxSynthesis of nanoplatelets
Preparing white calcium silicate hard nanowire powder into 0.1 wt% calcium silicate hard nanowire dispersion, and mixing 3 mmol cobalt chloride hexahydrate and chloride hexahydrateAdding nickel into 50mL of hard calcium silicate nanowire dispersion liquid, wherein the total concentration of cobalt ions and nickel ions is 0.06 mol/L, magnetically stirring for 0.5 h until the solution becomes transparent, carrying out water bath reaction for 3 h at the temperature of 80 ℃, cooling at room temperature, washing the obtained product for 3 times with water, washing for 1 time with ethanol, drying for 6 h in a vacuum drying oven at the temperature of 60 ℃, and preparing to obtain Co0.25Ni0.75（OH）2Nanosheet powder.
Adding 50 mg of sodium dihydrogen phosphite and 10 mg of Co into the head and tail of the small porcelain boat0.5Ni0.5（OH）2Heating the nanosheet powder to 300 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, and calcining at a high temperature to obtain Co0.25Ni0.75PxNanosheets.
2. Deposition of platinum monoatomic layer
6mg of Co are weighed0.25Ni0.75PxDispersing the nano-sheets in 2mL of isopropanol solution containing naphthol (the volume ratio of isopropanol to naphthol is 100: 1), ultrasonically dispersing for 1h, transferring 100mL of dispersed liquid drops on carbon paper with the thickness of 1 square centimeter by using a liquid transfer gun, and drying at room temperature; preparing sulfuric acid with a molar concentration of 0.5moL/L as an electrolyte and containing Co0.25Ni0.75PxThe carbon paper of the nano sheet is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the voltage range is set to be-0.2 to-1.0V, the number of circulation turns is respectively set to be 2500, 5000, 7500 and 10000, and the Pt-Co electrode is prepared0.25Ni0.75PxAnd (c) a complex.
For Pt-Co prepared in example 3 of the present invention0.25Ni0.75PxThe complexes were subjected to HER electrochemical testing.
Referring to FIG. 5, FIG. 5 shows 4 Pt-Co prepared in this example0.25Ni0.75PxLSV profile of HER of complex. It can be seen from the figure that HER performance is gradually increased with the increase of the number of cycles, the electrochemical performance is best when the number of cycles is 7500, and the improvement is remarkable compared with the improvement when the number of cycles is 0, 2500 and 5000, and HER electrochemical performance is also seen after the number of cycles is 7500The test performance becomes worse, which shows that the activity of the single atom deposition is the largest when the number of cycles is 7500, while the catalytic activity is reduced by the excessive deposition of the platinum atoms, which is the same as the law of the single atom catalytic activity, and the deposition process is laterally proved to be the deposition of one single atom.
Example 4
1、CoyPxSynthesis of nanoplatelets
Preparing 0.1 wt% hard calcium silicate nanowire dispersion from white hard calcium silicate nanowire powder, adding 3 mmol of cobalt chloride hexahydrate into 50mL of hard calcium silicate nanowire dispersion, wherein the concentration of cobalt ions is 0.06 mol/L, magnetically stirring for 0.5 h until the solution becomes transparent, carrying out water bath reaction for 3 h at the temperature of 80 ℃, cooling at room temperature, washing the obtained product for 3 times with water, washing for 1 time with ethanol, drying for 6 h in a vacuum drying oven at the temperature of 60 ℃, and preparing Co (OH)2Nanosheet powder.
Adding 50 mg of sodium dihydrogen phosphite and 10 mg of Co (OH) at the head and tail of the small porcelain boat2Heating the nanosheet powder to 300 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, and calcining at a high temperature to obtain CoyPxNanosheets.
2. Deposition of platinum monoatomic layer
6mg of Co are weighedyPxDispersing the nano-sheets in 2mL of isopropanol solution containing naphthol (the volume ratio of isopropanol to naphthol is 100: 1), ultrasonically dispersing for 1h, transferring 100mL of dispersed liquid drops on carbon paper with the thickness of 1 square centimeter by using a liquid transfer gun, and drying at room temperature; preparing sulfuric acid with a molar concentration of 0.5moL/L as an electrolyte and containing CoyPxThe carbon paper of the nano sheet is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the voltage range is set to be-0.2 to-1.0V, the number of circulating turns is set to be 7500, and the Pt-Co nano material is preparedyPxAnd (c) a complex.
For Pt-Co prepared in example 4 of the present inventionyPxThe complexes were subjected to HER electrochemical testing.
Referring to FIG. 6, FIG. 6 shows Pt-Co prepared in this exampleyPxLSV profile of HER of complex. The figure shows that after 7500 cycles, the HER electrochemical performance is obviously increased, which shows that the improvement of the electro-catalytic performance by the monatomic deposition is very obvious, and meanwhile, the preparation method of the invention can be applied to metal compounds with different proportions.
In summary, the invention provides a method for depositing platinum monoatomic atoms on the surface of metal phosphide nanosheets, which comprises the steps of adopting carbon paper loaded with the metal phosphide nanosheets as a working electrode, adopting a saturated calomel electrode as a reference electrode, adopting a platinum electrode as a counter electrode, setting a certain voltage and cycle number in an electrolyte, and further depositing the platinum monoatomic atoms on the metal phosphide nanosheets. The method disclosed by the invention does not need complex equipment, is simple to operate, has a wide application range, is suitable for various metal phosphide materials, remarkably improves the catalytic performance of the prepared compound, and provides a new thought for researching monatomic catalysis.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A method for depositing platinum monoatomic atoms on the surface of a metal phosphide nanosheet is characterized by comprising the following steps:
dispersing the metal phosphide nanosheets in a solvent to prepare a dispersion liquid;
dropping the dispersion liquid on carbon paper, drying to be used as a working electrode, taking a saturated calomel electrode as a reference electrode, and taking a platinum electrode as a counter electrode;
preparing electrolyte, setting up an electrolytic cell, setting a certain voltage and a certain number of circulating circles, and depositing platinum monoatomic ions on the surface of the metal phosphide nanosheets;
the metal elements in the metal phosphide nanosheets are one or more of VIII group metal elements, IVB group metal elements, VB group metal elements, VIB group metal elements, VIIB group metal elements and IIB group metal elements.
2. The method of claim 1, wherein the metal element in the metal phosphide nanosheets is one or more of iron, cobalt, nickel, manganese, zinc, chromium, tin, lead, and molybdenum.
3. The method of depositing platinum monatomics on the surface of metal phosphide nanosheets of claim 1, wherein the solvent is an isopropanol solution containing naphthol.
4. The method for depositing platinum monoatomic atoms on the surface of metal phosphide nanosheets according to claim 3, wherein the volume ratio of the isopropanol to the naphthol is 10:1 to 1000: 1.
5. The method for depositing platinum monoatomic atoms on the surface of metal phosphide nanosheets according to claim 1, wherein the dispersion has a mass concentration of 1-5 mg/mL.
6. The method of depositing platinum monatomics on the surface of metal phosphide nanoplates as recited in claim 1, wherein the carbon paper is 1 cm square carbon paper; and dropwise adding 50-500 mu L of the dispersion liquid on the carbon paper.
7. The method for depositing the platinum monoatomic atoms on the surfaces of the metal phosphide nanosheets according to claim 1, wherein the electrolyte is an acidic electrolyte with a pH of 1-3, a voltage of 0-1.3V and a number of cycles of 1000-15000 cycles.
8. A composite prepared by the method of any one of claims 1 to 7; the composite comprises metal phosphide nanosheets and platinum monatomics grown on the surface of the metal phosphide nanosheets.
9. Use of a compound according to claim 8 for electrocatalytic water splitting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810795400.4A CN109100402B (en) | 2018-07-19 | 2018-07-19 | Method for depositing platinum monoatomic compound and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810795400.4A CN109100402B (en) | 2018-07-19 | 2018-07-19 | Method for depositing platinum monoatomic compound and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109100402A CN109100402A (en) | 2018-12-28 |
| CN109100402B true CN109100402B (en) | 2020-10-27 |
Family
ID=64846916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810795400.4A Active CN109100402B (en) | 2018-07-19 | 2018-07-19 | Method for depositing platinum monoatomic compound and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109100402B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111197173B (en) * | 2020-02-07 | 2022-03-18 | 复旦大学 | Electroplating preparation method of non-noble metal single-atom-doped two-dimensional material |
| CN112774697B (en) * | 2020-09-07 | 2022-09-23 | 南京大学 | Monoatomic metal-molybdenum sulfide nano-composite and preparation method and application thereof |
| CN112023922B (en) * | 2020-09-27 | 2022-06-17 | 广州大学 | Pt-MnO2Material, preparation method and application thereof |
| CN113249739B (en) * | 2021-06-04 | 2022-07-15 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN114318403B (en) * | 2021-12-31 | 2023-08-25 | 上海大学 | Method for preparing platinum monoatomic material by adopting alkyl imidazole ionic liquid |
| CN114807996A (en) * | 2022-04-13 | 2022-07-29 | 北京工业大学 | Preparation method of monatomic platinum-loaded transition metal phosphide hydrogen evolution catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| CN106803534A (en) * | 2017-02-13 | 2017-06-06 | 东莞市佳乾新材料科技有限公司 | A kind of resistance-variable storing device based on indium phosphide resistive material and preparation method thereof |
| CN108067632A (en) * | 2016-11-11 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method for preparing noble metal orphan's atom in the solution and application |
-
2018
- 2018-07-19 CN CN201810795400.4A patent/CN109100402B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| CN108067632A (en) * | 2016-11-11 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method for preparing noble metal orphan's atom in the solution and application |
| CN106803534A (en) * | 2017-02-13 | 2017-06-06 | 东莞市佳乾新材料科技有限公司 | A kind of resistance-variable storing device based on indium phosphide resistive material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Highlights of the major pr ogress in single-atom catalysis in 2015 and 2016;Bing Han 等;《Chinese Journal of Catalysis》;20170905;第38卷(第9期);第1498-1507页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109100402A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109100402B (en) | Method for depositing platinum monoatomic compound and application | |
| Liu et al. | Amorphous Ni (OH) 2 encounter with crystalline CuS in hollow spheres: a mesoporous nano-shelled heterostructure for hydrogen evolution electrocatalysis | |
| Choi et al. | Reduced graphene oxide‐based materials for electrochemical energy conversion reactions | |
| Cardoso et al. | Reduced graphene oxide assembled Pd-based nanoalloys for hydrogen evolution reaction | |
| Hansu et al. | Hydrolysis and electrooxidation of sodium borohydride on novel CNT supported CoBi fuel cell catalyst | |
| CN108855184B (en) | High-performance oxygen evolution CoO @ Co-NC/C composite catalyst and preparation method and application thereof | |
| Yang et al. | Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction | |
| Qiu et al. | Selective conversion of CO2 to formate on a size tunable nano-Bi electrocatalyst | |
| CN109225301B (en) | Ir/Co0.8Fe0.2Se2-NF single-atom catalyst, preparation method and application thereof | |
| US9415379B2 (en) | Method of synthesizing tungsten carbide nanorods and catalysts formed therewith | |
| Nagashree et al. | Electrocatalytic oxidation of methanol on Ni modified polyaniline electrode in alkaline medium | |
| CN106925314B (en) | A kind of method of nickel assisted cryogenic synthesis molybdenum carbide elctro-catalyst | |
| CN113718281B (en) | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof | |
| CN113005469B (en) | Ruthenium-loaded amorphous nickel hydroxide/nickel phosphide composite electrode and preparation method and application thereof | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| CN114108004B (en) | Ruthenium-based alloy catalyst and preparation method and application thereof | |
| CN104549242A (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
| Oliveira et al. | Mesoporous graphitic carbon nitride-supported binary MPt (M: Co, Ni, Cu) nanoalloys as electrocatalysts for borohydride oxidation and hydrogen evolution reaction | |
| CN112517011A (en) | Carbon-based nickel-iron bimetal oxygen evolution catalyst and preparation method thereof | |
| CN109686990B (en) | Preparation method and application of Ni-Zn/nitrogen-sulfur double-doped three-dimensional graphene electrode material | |
| Li et al. | CoP-anchored high N-doped carbon@ graphene sheet as bifunctional electrocatalyst for efficient overall water splitting | |
| Wang et al. | Palygorskite promoted PtSn/carbon catalysts and their intrinsic catalytic activity for ethanol oxidation | |
| Xu et al. | The unified ordered mesoporous carbons supported Co-based electrocatalysts for full water splitting | |
| SUN et al. | Galvanic replacement strategy for a core-shell like Ni-Pt electrocatalyst with high Pt utilization | |
| Zhang et al. | Preparation of NiFeCr-based trimetal organic frameworks as electrocatalyst for direct use in oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |